A series of silyl-and germyl (dichloro) boranes Cl2B–ER3 (5, ER3= Si (SiMe3) 3; 6, ER3= Ge (SiMe3) 3; 7, ER3= Si (SiMe3) 2–Si (SiMe3) 3; 8, ER3= SiPh3) was obtained in good yields from the corresponding bis (dimethylamino) boranes (Me2N) 2B–ER3 (1, ER3= Si (SiMe3) 3; 2, ER3= Ge (SiMe3) 3; 3, ER3= Si (SiMe3) 2–Si (SiMe3) 3; 4, ER3= SiPh3) upon reaction with BCl3, and fully characterised in solution. These compounds proved to be versatile ...